Biphenyl-Derived Phosphepines as Chiral Nucleophilic Catalysts: Enantioselective [4+1] Annulations To Form Functionalized Cyclopentenes

Autor:	Takuya Ikeda, Yuji Fujiwara, Gregory C. Fu, Daniel T. Ziegler, Lorena Riesgo
Přispěvatelé:	Massachusetts Institute of Technology. Department of Chemistry, Ziegler, Daniel Todd, Riesgo Canal, Lorena, Ikeda, Takuya, Fujiwara, Yuji, Fu, Gregory C
Rok vydání:	2014
Předmět:	Models Molecular Annulation Chemistry Stereochemistry Phosphines Enantioselective synthesis Stereoisomerism General Medicine General Chemistry Cyclopentanes Catalysis Article Stereocenter chemistry.chemical_compound Nucleophile Catalytic cycle Cyclization Organocatalysis Stereoselectivity Phosphine
Zdroj:	PMC
Popis:	Because of the frequent occurrence of cyclopentane subunits in bioactive compounds, the development of efficient catalytic asymmetric methods for their synthesis is an important objective. Introduced herein is a new family of chiral nucleophilic catalysts, biphenyl-derived phosphepines, and we apply them to an enantioselective variant of a useful [4+1] annulation. A range of one-carbon coupling partners can be employed, thereby generating cyclopentenes which bear a fully substituted stereocenter [either all-carbon or heteroatom-substituted (sulfur and phosphorus)] . Stereocenters at the other four positions of the cyclopentane ring can also be introduced with good stereoselectivity. An initial mechanistic study indicates that phosphine addition to the electrophilic fourcarbon coupling partner is not the turnover-limiting step of the catalytic cycle. National Institutes of Health (U.S.) (Grant R01-GM57034)
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::286e80944fb7c276df1f8fa82d4e6013 http://hdl.handle.net/1721.1/113310 Zobrazit plný text záznamu